Dishwashing method

ABSTRACT

A method of washing dishware/tableware in an automatic dishwashing machine, the method comprising simultaneously or sequentially delivering quantities of a particulate or densified particulate automatic dishwashing product and of an anhydrous liquid, gel or paste form dishwashing detergent auxiliary contained in separate compartments of a multi-compartment pouch into the same or different cycles of the dishwashing machine. The method provides improved cleaning performance and product stability.

TECHNICAL FIELD

[0001] The present invention is in the field of dishwashing, inparticular it relates to dishwashing methods including methods forwashing dishware/tableware in an automatic dishwashing machine usingdishwashing products in multi-compartment pouch form. The methods of theinvention provide excellent cleaning results.

BACKGROUND OF THE INVENTION

[0002] Unitised doses of dishwashing detergents are found to be moreattractive and convenient to some consumers because they avoid the needof the consumer to measure the product thereby giving rise to a moreprecise dosing and avoiding wasteful overdosing or underdosing. For thisreason automatic dishwashing detergent products in tablet form havebecome very popular. Detergent products in pouch form are also known inthe art.

[0003] It is well known to use bleach in dishwashing detergentformulations in order to remove stains, especially tea, coffee, fruitjuice and carotenoid stains. Chlorine and peroxygen bleaches areeffective for stain removal. While chlorine bleach is a very effectivecleaning agent, it is not compatible with a variety of detergentingredients and may require additional processing in order to beincorporated into a final product. Peroxide bleaches on the other handare more compatible with conventional detergent ingredients. However,one of the problems found when formulating peroxygen containingdishwashing detergent compositions is the fact that the bleach is liableto decompose in contact with moisture, thereby reducing the amount ofactive bleach available for the dishwashing process. Once thedecomposition process is initiated, moreover, decomposition is autocatalysed by the presence of free radicals generated by thedecomposition process. The products of bleach decomposition can alsooxidise detergency enzymes, thereby reducing the amount of enzymeavailable for the dishwashing process.

[0004] In the case of flexible unitised doses such as pouches, capsulesor sachets which are moisture permeable, bleach decomposition gives riseto an additional problem due to the generation of gaseous oxygen.Usually the pouch material is not permeable to oxygen and this can leadto bloating or even destruction of the pouch and to a detrimental effecton appearance and on dispenser fit.

[0005] Some detergent ingredients used in dishwashing detergentcompositions are liquids. These liquid ingredients can be difficult orcostly to include in a solid detergent composition. Also, certainingredients are preferably transported and supplied to detergentmanufacturers in a liquid form and require additional, and sometimescostly, process steps to enable them to be included in a solid detergentcomposition. An example of these detergent ingredients are surfactants,especially nonionic surfactants which are typically liquid at roomtemperature or are typically transported and supplied to detergentmanufacturers in liquid form. Another example are organic solvents.

[0006] Current methods of incorporating liquid ingredients into soliddetergent compositions include absorbing the liquid ingredient onto asolid carrier, for example by mixing, agglomeration or spray-ontechniques. Typically, solid detergent compositions comprise only lowamounts of these liquid detergent ingredients due to the difficulty andexpense of incorporating these liquid ingredients into a soliddetergent. The problems are particularly acute in the case of solidcompositions which are subject to a densification step and especially tothe levels of densification applied in machine dishwashing tabletmanufacture. Furthermore, the incorporation of liquid ingredients intosolid detergent compositions can impact on the dissolutioncharacteristics of the composition (for example as the result of formingsurfactant gel phases) and can also lead to problems of flowability. Itwould be advantageous to have a detergent composition which allows thedifferent ingredients to be in their natural state i.e., liquid orsolid. This would facilitate the manufacturing process and furthermoreallow the delivery of liquid ingredients prior or post to the deliveryof solid ingredients. For example differential dissolution of activeingredients would be beneficial in the case of enzyme/bleachcompositions to avoid oxidation of enzymes by the bleach in thedishwashing liquor. It would also be advantageous to separate bleachfrom perfume.

[0007] An objective of the present invention is to provide dishwashingmethods and products delivering improved cleaning performance andproduct stability. Another object is to provide dishwashing methods andproducts which have simplified processing, which allow for the problemsof product incompatibility and which are capable of providingdifferential dissolution of active components.

SUMMARY OF THE INVENTION

[0008] According to a first aspect of the present invention, there isprovided a method of washing dishware/tableware in an automaticdishwashing machine, the method comprising simultaneously orsequentially delivering quantities of a particulate or densifiedparticulate automatic dishwashing product and of an anhydrous liquid,gel or paste form dishwashing detergent auxiliary contained in separatecompartments of a multi-compartment pouch into the same or differentcycles of the dishwashing machine.

[0009] Suitable multi-compartment pouches (which term includes capsules,sachets and other compartmentalized unit dose containers) for use hereininclude water-soluble, water-dispersible and water-permeable pouches.Preferred for use herein are water soluble pouches, based on partiallyhydrolysed polyvinylacetate/polyvinyl alcohol as pouch material.Although, soluble in water, these pouches have the disadvantage thatthey are permeable to moisture.

[0010] The term anhydrous as used herein is intended to includecompositions containing less than about 10% of water by weight of thecomposition, preferably less than about 5% of water and more preferablyless than about 1%. The water can be present in the form of hydratedcompounds, i.e. bound water or in the form of moisture. It is preferredthat the composition contains less than about 1%, preferably less thanabout 0.1% free moisture. Free moisture can be measured by extracting 2g of the product into 50 ml of dry methanol at room temperature for 20minutes and then analysis a 1 ml aliquot of the methanol by Karl Fischertitration. The term water-soluble as used to describe the pouch meansthat the pouch or a compartment thereof dissolves or disperses in waterto release some or all of the contents thereof at some temperature orrange of temperatures in the normal operating range of a dishwashingmachine (ambient to 70° C.). Under other temperatures or conditions ofuse, however, the pouch or compartment thereof may be insoluble inwater, remaining intact for extended periods greater than that of thenormal operating regime of the dishwashing machine.

[0011] In a preferred embodiment the particulate dishwashing product isdensified. Densification can be achieved by compaction, compression,tamping, tapping, stamping, vibrating, subjecting to inertial forces,etc, densification being preferably such as to provide a bulk densityincrease of at least about 10%, preferably at least about 20%, morepreferably at least about 30%. The final bulk density is preferably atleast about 0.6 g/cc, more preferably at least about 0.8 g/cc,especially at least about 1 g/cc, and more especially at least about 1.3g/cc.

[0012] In a preferred embodiment, the densified particulate dishwashingproduct is in the form of a tablet. Multi-compartment pouches comprisinga tablet and an anhydrous liquid, gel or paste present the knownadvantages of tablets, such as high product density, minimum storagevolume requirements and efficient packing, but they also allow for thesimultaneous or sequential release of a liquid, gel or paste inquantities which it would be impossible to achieve through normaltabletting techniques. A further advantage of said pouches is that theuser does not touch or come into direct contact with the tablet and theremainder of the automatic dishwashing composition.

[0013] From the manufacturing viewpoint, multi-compartment pouchescomprising a particulate automatic dishwashing product in the form of atablet are very convenient because the filling of pouches withparticulate product can be complex and prone to inaccuracies. It isoften slow and likely to produce dust, such that it can be verydifficult to avoid dust deposition on the pouch seal area. This can bedetrimental to achieving a strong seal.

[0014] The tablet can be formed using any suitable method, butpreferably by compression, for example in a tablet press. Preferably,the tablet is a compressed shaped body prepared by mixing together thecomponents of the automatic dishwashing detergent followed by applying acompression pressure of at least about 40 kg/cm², preferably at leastabout 250 kg/cm², more preferably at least about 350 kg/cm² (3.43kN/cm²), even more preferably from about 400 to about 2000, andespecially from about 600 to about 1200 kg/cm² (compression pressureherein is the applied force divided by the cross-sectional area of thetablet in a plane transverse to the applied force—in effect, thetransverse cross-sectional area of the die of the rotary press). Suchtablets being preferred herein from the viewpoint of providing optimumtablet integrity and strength (measured for example by the Child BiteStrength [CBS] test) and product dissolution characteristics. Thetablets preferably have a CBS of at least about 6 kg, preferably greaterthan about 8 kg, more preferably greater than about 10 kg, especiallygreater than about 12 kg, and more especially greater than about 14 kg,CBS being measured per the US Consumer Product Safety Commission TestSpecification.

[0015] The tablet can take a variety of geometric shapes such asspheres, cubes, etc but preferably has a generally axially-symmetricform with a generally round, square or rectangular cross-section.

[0016] The tablet can be prepared such that it comprises at least onemould in its surface. The mould or moulds can also vary in size andshape and in their location, orientation and topology relative to thetablet. For example, the mould or moulds can be generally circular,square or oval in cross-section; they can form an internally-closedcavity, depresion or recess in the surface of the tablet, or they canextend between unconnected regions of the tablet surface (for exampleaxially-opposed facing surfaces) to form one or more topological ‘holes’in the tablet; and they can be axially or otherwisesymmetrically-disposed relative to the tablet or they can beasymmetrically disposed. Preferably, the mould is preformed, for examplebeing created using a specially designed tablet press wherein thesurface of the punch that contacts the detergent composition is shapedsuch that when it contacts and presses the detergent composition itpresses a mould, or multiple moulds into the detergent tablet.Preferably, the mould will have an inwardly concave or generally concavesurface to provide improved housing and physical storage of the liquid,gel or paste containing compartment. Alternatively, the mould can becreated by compressing a preformed body of detergent compositiondisposed annularly around a central dye, thereby forming a shaped bodyhaving a mould in the form of a cavity extending axially betweenopposing surfaces of the body. Tablets with moulds are very useful fromthe viewpoint of accommodating the compartment comprising the anhydrousliquid, gel or paste dishwashing detergent auxiliary of the presentinvention.

[0017] According to a preferred embodiment of the present invention, theparticulate dishwashing product comprises one or more moisture-sensitivedetergent actives and the detergent auxiliary comprises a humectant inlevels sufficient to act as a moisture sink for stabilising themoisture-sensitive detergent active. A detergent active is considered tobe moisture-sensitive when it can interact with moisture to decrease itsdetergency activity as for example detergency bleach. Particulatebleaches suitable for use herein include inorganic peroxides inclusiveof perborates and percarbonates, organic peracids inclusive of preformedmonoperoxy carboxylic acids, such as phthaloyl amido peroxy hexanoicacid and di-acyl peroxides. Preferred peroxides for use herein arepercarbonate and perborate bleach.

[0018] Humectant is a substance which can pick up or emit moisture tothe surroundings depending on the surrounding relative humidity. Whenformulated as part of the detergent auxiliary, the humectants usedherein are capable of acting as moisture sink for the powder layer. Thisstabilises the moisture-sensitive detergent active. The humectantsshould have a humidity equilibrium point such as to enable them to actas moisture sink but preferably they should take up less than about 10%,more preferably less than about 5% even more preferably less than about1% of water at a relative humidity of 50% or less, preferably atrelative humidity of 75% or less, and more preferably at relativehumidity of 90% or less under ambient conditions of temperature andpressure (20° C. and 1 atmosphere). Humectants suitable for use hereininclude non-aqueous hydrophilic organic solvents inclusive of glycolsand polyhydric alcohols, for example sorbitol, glycerol, dipropyleneglycol and mixtures thereof, and also various hygroscopic solidsinclusive of inorganic or organic salts such as silicates, phosphatesand citrates, as well as sugars, etc. Preferred for use herein arehumectants and humectant mixtures comprising glycols, more preferablypolyethylene glycols and especially mixtures of polyethylene glycols ofdifferent molecular weight. For example, mixtures of polyethylene glycolhaving a molecular weight of about 200 to about 1,200, more preferablyfrom about 200 to about 800 and polyethylene glycol having a molecularweight of about 2,000 to about 6,000 more preferably from about 2,600 toabout 4,000. In the mixtures of polyethylene glycol used herein the lowmolecular weight and the high molecular weight polyethylene glycol areusually in a weight ratio of at least 10:1 and preferably at least 100:1.

[0019] In a preferred embodiment, the anhydrous detergent auxiliarycomposition comprises a detergency enzyme. The enzyme is preferably inliquid form and is delivered to the wash liquor substantially prior tothe particulate products, thereby minimizing or avoiding interactionwith actives, such as bleach, which can have a deleterious effect onenzyme stability and performance in the wash solution.

[0020] In preferred embodiments the dishwashing composition comprises anorganic solvent system. The organic solvent system can simply act as aliquid carrier, but in preferred compositions, the solvent can aidremoval of cooked-, baked- or burnt-on soil and thus has detergentfunctionality in its own right. The organic solvent system (comprising asingle solvent compound or a mixture of solvent compounds) preferablyhas a volatile organic content above 1 mm Hg and more preferably above0.1 mm Hg of less than about 50%, preferably less than about 20% andmore preferably less than about 10% by weight of the solvent system.Herein volatile organic content of the solvent system is defined as thecontent of organic components in the solvent system having a vaporpressure higher than the prescribed limit at 25° C. and atmosphericpressure. The organic solvent system for use herein is preferablyselected from organoamine solvents, inclusive of alkanolamines,alkylamines, alkyleneamines and mixtures thereof; alcoholic solventsinclusive of aromatic, aliphatic (preferably C₄-C₁₀) and cycloaliphaticalcohols and mixtures thereof; glycols and glycol derivatives inclusiveof C₂-C₃ (poly)alkylene glycols, glycol ethers, glycol esters andmixtures thereof; and mixtures selected from organoamine solvents,alcoholic solvents, glycols and glycol derivatives. In one preferredembodiment the organic solvent comprises organoamine (especiallyalkanolamine) solvent and glycol ether solvent, preferably in a weightratio of from about 3:1 to about 1:3, and wherein the glycol ethersolvent is selected from ethylene glycol monobutyl ether, diethyleneglycol monobutyl ether, ethylene glycol monomethyl ether, ethyleneglycol monoethyl ether, diethylene glycol monomethyl ether, diethyleneglycol monoethyl ether, propylene glycol monobutyl ether, and mixturesthereof. Preferably, the glycol ether is a mixture of diethylene glycolmonobutyl ether and propylene glycol butyl ether, especially in a weightratio of from about 1:2 to about 2:1.

[0021] According to another embodiment of the invention the dishwashingauxiliary composition can take the form of a paste having a densitygreater than about 1100 Kg/m³, preferably greater than about 1300 Kg/m³.

[0022] Multi-compartment pouches suitable for use herein can includecompartments with different solubility profiles controlled by forexample pH, temperature or any other means. High temperaturewater-soluble pouches allow handling of the pouches at ambienttemperature with wet hands.

[0023] The multi-compartment pouches herein comprise at least onecompartment containing a powder or densified powder composition and atleast one containing an anhydrous liquid, gel or paste. This powdercomposition comprises traditional solid materials used in dishwashingdetergent, such as builders, alkalinity sources, together withmoisture-sensitive detergent active such as bleaches, etc. The liquid,gel or paste compositions comprise traditional liquid materials used indishwashing detergents, such as non-ionic surfactants or the organicsolvents described hereinabove together with a humectant. Preferably thecompartment comprising the detergent auxiliary is placed above oradjacent the compartment comprising the moisture-sensitive detergentactive in order to help protect the moisture-sensitive detergent activeand to reduce the surface area of the pouch containing compartment whichis exposed to moisture.

DETAILED DESCRIPTION OF THE INVENTION

[0024] The present invention envisages the use of dishwashing detergentand auxiliary compositions in a multi-compartment pouch, whereby amoisture-sensitive detergent active and a humectant are contained inseparate compartments. The humectant is capable of acting as a moisturesink and acts to stabilize the moisture-sensitive detergent active.

[0025] Unitised dose forms specially useful for use herein are pouches.The pouch herein is typically a closed structure which comprises two ormore compartments, made of materials described herein. Subject to theconstraints of dispenser fit, the pouch can be of any form, shape andmaterial which is suitable to hold the composition, e.g. withoutallowing the release of the composition from the pouch prior to contactof the pouch to water. The exact execution will depend on, for example,the type and amount of the composition in the pouch, the number ofcompartments in the pouch, the characteristics required from the pouchto hold, protect and deliver or release the composition and/orcomponents thereof.

[0026] The composition, or components thereof, are contained in theinternal volume space of the pouch, and are typically separated from theoutside environment by a barrier of water-soluble material. Typically,different components of the composition contained in differentcompartments of the pouch are separated from one another by a barrier ofwater-soluble material.

[0027] In the case of multi-compartment pouches, the compartments may beof a different colour from each other, for example a first compartmentmay be green or blue, and a second compartment may be white or yellow.One compartment of the pouch may be opaque or semi-opaque, and a secondcompartment of the pouch may be translucent, transparent, orsemi-transparent. The compartments of the pouch may be the same size,having the same internal volume, or may be different sizes havingdifferent internal volumes.

[0028] For reasons of deformability and dispenser fit under compressionforces, pouches or pouch compartments containing a component which isliquid will usually contain an air bubble having a volume of up to about50%, preferably up to about 40%, more preferably up to about 30%, morepreferably up to about 20%, more preferably up to about 10% of thevolume space of said compartment.

[0029] The pouch is preferably made of a pouch material which is solubleor dispersible in water, and preferably has a water-solubility of atleast 50%, preferably at least 75% or even at least 95%, as measured bythe method set out hereafter using a glass-filter with a maximum poresize of 20 microns.

[0030] 50 grams±0.1 gram of pouch material is added in a pre-weighed 400ml beaker and 245 ml±1 ml of distilled water at the appropriatetemperature is added. This is stirred vigorously on a heatable platewith a magnetic stirrer set at 600 rpm, for 30 minutes. Then, themixture is filtered through a folded qualitative sintered-glass filterwith a pore size as defined above (max. 20 micron). The water is driedoff from the collected filtrate by any conventional method, and theweight of the remaining material is determined (which is the dissolvedor dispersed fraction). Then, the % solubility or dispersability at thespecified temperature can be calculated.

[0031] Preferred pouch materials are polymeric materials, preferablypolymers which are formed into a film or sheet. The pouch material can,for example, be obtained by casting, blow-moulding, extrusion or blowextrusion of the polymeric material, as known in the art.

[0032] Preferred polymers, copolymers or derivatives thereof suitablefor use as pouch material are selected from polyvinyl alcohols,partially hydrolysed polyvinylacetates, polyvinyl pyrrolidone,polyalkylene oxides, acrylamide, acrylic acid, cellulose, celluloseethers, cellulose esters, cellulose amides, polyvinyl acetates,polycarboxylic acids and salts, polyaminoacids or peptides, polyamides,polyacrylamide, copolymers of maleic/acrylic acids, polysaccharidesincluding starch and gelatine, natural gums such as xanthum andcarragum. More preferred polymers are selected from polyacrylates andwater-soluble acrylate copolymers, methylcellulose,carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose,maltodextrin, polymethacrylates, and most preferably selected frompolyvinyl alcohols, polyvinyl alcohol copolymers, partially hydrolysedpolyvinylacetates and hydroxypropyl methyl cellulose (HPMC),hydroxybutyl methylcellulose (HBMC), and combinations thereof.Preferably, the level of polymer in the pouch material, for example aPVA polymer, is at least 60%.

[0033] The polymer can have any weight average molecular weight,preferably from about 1000 to 1,000,000, more preferably from about10,000 to 300,000 yet more preferably from about 20,000 to 150,000.

[0034] Mixtures of polymers can also be used as the pouch material. Thiscan be beneficial to control the mechanical and/or dissolutionproperties of the compartments or pouch, depending on the applicationthereof and the required needs. Suitable mixtures include for examplemixtures wherein one polymer has a higher water-solubility than anotherpolymer, and/or one polymer has a higher mechanical strength thananother polymer. Also suitable are mixtures of polymers having differentweight average molecular weights, for example a mixture of PVA or acopolymer thereof of a weight average molecular weight of about10,000-40,000, preferably around 20,000, and of PVA or copolymerthereof, with a weight average molecular weight of about 100,000 to300,000, preferably around 150,000.

[0035] Also suitable herein are polymer blend compositions, for examplecomprising hydrolytically degradable and water-soluble polymer blendssuch as polylactide and polyvinyl alcohol, obtained by mixingpolylactide and polyvinyl alcohol, typically comprising about 1-35% byweight polylactide and about 65% to 99% by weight polyvinyl alcohol.

[0036] Preferred for use herein are polymers inclusive ofpolyvinylacetate which are from about 60% to about 98% hydrolysed,preferably about 80% to about 90% hydrolysed, to improve the dissolutioncharacteristics of the material.

[0037] Most preferred pouch materials are PVA films known under thetrade reference Monosol M8630, as sold by Chris-Craft IndustrialProducts of Gary, Ind., US, and PVA films of corresponding solubilityand deformability characteristics. Other films suitable for use hereininclude films known under the trade reference PT film or the K-series offilms supplied by Aicello, or VF-HP film supplied by Kuraray.

[0038] The pouch material herein can also comprise one or more additiveingredients. For example, it can be beneficial to add plasticisers, forexample glycerol, ethylene glycol, diethyleneglycol, propylene glycol,sorbitol and mixtures thereof. Other additives include functionaldetergent additives to be delivered to the wash water, for exampleorganic polymeric dispersants, etc.

[0039] The pouch can be prepared according to methods known in the art.The pouch is typically prepared by first cutting an appropriately sizedpiece of pouch material, preferably the pouch material. The pouchmaterial is then folded to form the necessary number and size ofcompartments and the edges are sealed using any suitable technology, forexample heat sealing, wet sealing or pressure sealing. Preferably, asealing source is brought into contact with the pouch material, heat orpressure is applied and the pouch material is sealed.

[0040] The pouch material is typically introduced to a mould and avacuum applied so that the pouch material is flush with the innersurface of the mould, thus forming a vacuum formed indent or niche insaid pouch material. This is referred to as vacuum-forming.

[0041] Another suitable method is thermo-forming. Thermo-formingtypically involves the step of forming an open pouch in a mould underapplication of heat, which allows the pouch material to take on theshape of the mould.

[0042] Typically more than one piece of pouch material is used formaking multi-compartment pouches. For example, a first piece of pouchmaterial can be vacuum pulled into the mould so that said pouch materialis flush with the inner walls of the mould. A second piece of pouchmaterial can then be positioned such that it at least partiallyoverlaps, and preferably completely overlaps, with the first piece ofpouch material. The first piece of pouch material and second piece ofpouch material are sealed together. The first piece of pouch materialand second piece of pouch material can be made of the same type ofmaterial or can be different types of material.

[0043] In a preferred process, a piece of pouch material is folded atleast twice, or at least three pieces of pouch material are used, or atleast two pieces of pouch material are used wherein at least one pieceof pouch material is folded at least once. The third piece of pouchmaterial, or a folded piece of pouch material, creates a barrier layerthat, when the sachet is sealed, divides the internal volume of saidsachet into at least two or more compartments.

[0044] The pouch can also be prepared by fitting a first piece of thepouch material into a mould, for example the first piece of film may bevacuum pulled into the mould so that said film is flush with the innerwalls of the mould. A composition, or component thereof, is typicallypoured into the mould. A pre-sealed compartment made of pouch material,is then typically placed over the mould containing the composition, orcomponent thereof. The pre-sealed compartment preferably contains acomposition, or component thereof. The pre-sealed compartment and saidfirst piece of pouch material may be sealed together to form the pouch.

[0045] The detergent auxiliary herein can comprise traditionaldetergency components and can also comprise organic solvents having acleaning function and organic solvents having a carrier or diluentfunction or some other specialised function. The compositions willgenerally be built and comprise one or more detergent active componentswhich may be selected from colorants, bleaching agents, surfactants,alkalinity sources, enzymes, thickeners (in the case of liquid, paste,cream or gel compositions), anti-corrosion agents (e.g. sodium silicate)and disrupting and binding agents (in the case of powder, granules ortablets). Highly preferred detergent auxiliary components include abuilder compound, an alkalinity source, a surfactant, an enzyme and ableaching agent.

[0046] Unless otherwise specified, the components described hereinbelowcan be incorporated either in the automatic dishwashing product ordetergent auxiliary.

[0047] The organic solvents should be selected so as to be compatiblewith the tableware/cookware as well as with the different parts of anautomatic dishwashing machine. Furthermore, the solvent system should beeffective and safe to use having a volatile organic content above 1 mmHg (and preferably above 0.1 mm Hg) of less than about 50%, preferablyless than about 30%, more preferably less than about 10% by weight ofthe solvent system. Also they should have very mild pleasant odours. Theindividual organic solvents used herein generally have a boiling pointabove about 150° C., flash point above about 100° C. and vapor pressurebelow about 1 mm Hg, preferably below 0.1 mm Hg at 25° C. andatmospheric pressure.

[0048] Solvents that can be used herein include: i) alcohols, such asbenzyl alcohol, 1,4-cyclohexanedimethanol, 2-ethyl-1-hexanol, furfurylalcohol, 1,2-hexanediol and other similar materials; ii) amines, such asalkanolamines (e.g. primary alkanolamines: monoethanolamine,monoisopropanolamine, diethylethanolamine, ethyl diethanolamine;secondary alkanolamines: diethanolamine, diisopropanolamine,2-(methylamino)ethanol; ternary alkanolamines: triethanolamine,triisopropanolamine); alkylamines (e.g. primary alkylamines:monomethylamine, monoethylamine, monopropylamine, monobutylamine,monopentylamine, cyclohexylamine), secondary alkylamines:(dimethylamine), alkylene amines (primary alkylene amines:ethylenediamine, propylenediamine) and other similar materials; iii)esters, such as ethyl lactate, methyl ester, ethyl acetoacetate,ethylene glycol monobutyl ether acetate, diethylene glycol monoethylether acetate, diethylene glycol monobutyl ether acetate and othersimilar materials; iv) glycol ethers, such as ethylene glycol monobutylether, diethylene glycol monobutyl ether, ethylene glycol monomethylether, ethylene glycol monoethyl ether, diethylene glycol monomethylether, diethylene glycol monoethyl ether, propylene glycol butyl etherand other similar materials; v) glycols, such as propylene glycol,diethylene glycol, hexylene glycol (2-methyl-2,4 pentanediol),triethylene glycol, composition and dipropylene glycol and other similarmaterials; and mixtures thereof.

[0049] Surfactant

[0050] In the methods of the present invention, the detergent surfactantis preferably low foaming by itself or in combination with othercomponents (i.e. suds suppressers). Surfactants suitable herein includeanionic surfactants such as alkyl sulfates, alkyl ether sulfates, alkylbenzene sulfonates, alkyl glyceryl sulfonates, alkyl and alkenylsulphonates, alkyl ethoxy carboxylates, N-acyl sarcosinates, N-acyltaurates and alkyl succinates and sulfosuccinates, wherein the alkyl,alkenyl or acyl moiety is C₅-C₂₀, preferably C₁₀-C₁₈ linear or branched;cationic surfactants such as chlorine esters (U.S. Pat. No. 4,228,042,U.S. Pat. No. 4,239,660 and U.S. Pat. No. 4,260,529) and mono C₆-C₁₆N-alkyl or alkenyl ammonium surfactants wherein the remaining Npositions are substituted by methyl, hydroxyethyl or hydroxypropylgroups; low and high cloud point nonionic surfactants and mixturesthereof including nonionic alkoxylated surfactants (especiallyethoxylates derived from C₆-C₁₈ primary alcohols),ethoxylated-propoxylated alcohols (e.g., Olin Corporation'sPoly-Tergent® SLF18), epoxy-capped poly(oxyalkylated) alcohols (e.g.,Olin Corporation's Poly-Tergent® SLF18B—see WO-A-94/22800), ether-cappedpoly(oxyalkylated) alcohol surfactants, and blockpolyoxyethylene-polyoxypropylene polymeric compounds such as PLURONIC®,REVERSED PLURONIC®, and TETRONIC® by the BASF-Wyandotte Corp.,Wyandotte, Mich.; amphoteric surfactants such as the C₁₂-C₂₀ alkyl amineoxides (preferred amine oxides for use herein include lauryldimethylamine oxide and hexadecyl dimethyl amine oxide), and alkylamphocarboxylic surfactants such as Miranol™ C2M; and zwitterionicsurfactants such as the betaines and sultaines; and mixtures thereof.Surfactants suitable herein are disclosed, for example, in U.S. Pat. No.3,929,678, U.S. Pat. No. 4,259,217, EP-A-0414 549, WO-A-93/08876 andWO-A-93/08874. Surfactants are typically present at a level of fromabout 0.2% to about 30% by weight, more preferably from about 0.5% toabout 10% by weight, most preferably from about 1% to about 5% by weightof composition. Preferred surfactant for use herein are low foaming andinclude low cloud point nonionic surfactants and mixtures of higherfoaming surfactants with low cloud point nonionic surfactants which actas suds suppresser therefor.

[0051] Builder

[0052] Builders suitable for use in detergent and cleaning compositionsherein include water-soluble builders such as citrates, carbonates andpolyphosphates e.g. sodium tripolyphosphate and sodium tripolyphosphatehexahydrate, potassium tripolyphosphate and mixed sodium and potassiumtripolyphosphate salts; and partially water-soluble or insolublebuilders such as crystalline layered silicates (EP-A-0164514 andEP-A-0293640) and aluminosilicates inclusive of Zeolites A, B, P, X, HSand MAP. The builder is typically present at a level of from about 1% toabout 80% by weight, preferably from about 10% to about 70% by weight,most preferably from about 20% to about 60% by weight of composition.

[0053] Amorphous sodium silicates having an SiO₂:Na₂O ratio of from 1.8to 3.0, preferably from 1.8 to 2.4, most preferably 2.0 can also be usedherein although highly preferred from the viewpoint of long term storagestability are compositions containing less than about 22%, preferablyless than about 15% total (amorphous and crystalline) silicate.

[0054] Enzyme

[0055] Enzymes suitable herein include bacterial and fungal cellulasessuch as Carezyme and Celluzyme (Novo Nordisk A/S); peroxidases; lipasessuch as Amano-P (Amano Pharmaceutical Co.), M1 Lipase® and Lipomax®(Gist-Brocades) and Lipolase® and Lipolase Ultra® (Novo); cutinases;proteases such as Esperase®, Alcalase®, Durazym® and Savinase® (Novo)and Maxatase®, Maxacal®, Properase® and Maxapem® (Gist-Brocades); and αand β amylases such as Purafect Ox Am® (Genencor) and Termamyl®, Ban®,Fungamyl®, Duramyl®, and Natalase® (Novo); and mixtures thereof. Enzymesare preferably added herein as prills, granulates, or cogranulates atlevels typically in the range from about 0.0001% to about 2% pure enzymeby weight of composition.

[0056] Bleaching agent

[0057] Bleaching agents suitable herein include chlorine and oxygenbleaches, especially inorganic perhydrate salts such as sodium perboratemono-and tetrahydrates and sodium percarbonate optionally coated toprovide controlled rate of release (see, for example, GB-A-1466799 onsulfate/carbonate coatings), preformed organic peroxyacids and mixturesthereof with organic peroxyacid bleach precursors and/or transitionmetal-containing bleach catalysts (especially manganese or cobalt).Inorganic perhydrate salts are typically incorporated at levels in therange from about 1% to about 40% by weight, preferably from about 2% toabout 30% by weight and more preferably from abut 5% to about 25% byweight of composition. Peroxyacid bleach precursors preferred for useherein include precursors of perbenzoic acid and substituted perbenzoicacid; cationic peroxyacid precursors; peracetic acid precursors such asTAED, sodium acetoxybenzene sulfonate and pentaacetylglucose;pernonanoic acid precursors such as sodium3,5,5-trimethylhexanoyloxybenzene sulfonate (iso-NOBS) and sodiumnonanoyloxybenzene sulfonate (NOBS); amide substituted alkyl peroxyacidprecursors (EP-A-0170386); and benzoxazin peroxyacid precursors(EP-A-0332294 and EP-A-0482807). Bleach precursors are typicallyincorporated at levels in the range from about 0.5% to about 25%,preferably from about 1% to about 10% by weight of composition while thepreformed organic peroxyacids themselves are typically incorporated atlevels in the range from 0.5% to 25% by weight, more preferably from 1%to 10% by weight of composition. Bleach catalysts preferred for useherein include the manganese triazacyclononane and related complexes(U.S. Pat. No. 4,246,612, U.S. Pat. No. 5,227,084); Co, Cu, Mn and Febispyridylamine and related complexes (U.S. Pat. No. 5,114,611); andpentamine acetate cobalt(III) and related complexes(U.S. Pat. No.4,810,410).

[0058] Low cloud point non-ionic surfactants and suds suppressers

[0059] The suds suppressers suitable for use herein include nonionicsurfactants having a low cloud point. “Cloud point”, as used herein, isa well known property of nonionic surfactants which is the result of thesurfactant becoming less soluble with increasing temperature, thetemperature at which the appearance of a second phase is observable isreferred to as the “cloud point” (See Kirk Othmer, pp. 360-362). As usedherein, a “low cloud point” nonionic surfactant is defined as a nonionicsurfactant system ingredient having a cloud point of less than 30° C.,preferably less than about 20° C., and even more preferably less thanabout 10° C., and most preferably less than about 7.5° C. Typical lowcloud point nonionic surfactants include nonionic alkoxylatedsurfactants, especially ethoxylates derived from primary alcohol, andpolyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverseblock polymers. Also, such low cloud point nonionic surfactants include,for example, ethoxylated-propoxylated alcohol (e.g., Olin Corporation'sPoly-Tergent® SLF18) and epoxy-capped poly(oxyalkylated) alcohols (e.g.,Olin Corporation's Poly-Tergent® SLF18B series of nonionics, asdescribed, for example, in U.S. Pat. No. 5,576,281).

[0060] Preferred low cloud point surfactants are the ether-cappedpoly(oxyalkylated) suds suppresser having the formula:

[0061] wherein R¹ is a linear, alkyl hydrocarbon having an average offrom about 7 to about 12 carbon atoms, R² is a linear, alkyl hydrocarbonof about 1 to about 4 carbon atoms, R³ is a linear, alkyl hydrocarbon ofabout 1 to about 4 carbon atoms, x is an integer of about 1 to about 6,y is an integer of about 4 to about 15, and z is an integer of about 4to about 25.

[0062] Other low cloud point nonionic surfactants are the ether-cappedpoly(oxyalkylated) having the formula:

R_(I)O(R_(II)O)_(n)CH(CH₃)OR_(III)

[0063] wherein, R_(I) is selected from the group consisting of linear orbranched, saturated or unsaturated, substituted or unsubstituted,aliphatic or aromatic hydrocarbon radicals having from about 7 to about12 carbon atoms; R_(II) may be the same or different, and isindependently selected from the group consisting of branched or linearC₂ to C₇ alkylene in any given molecule; n is a number from 1 to about30; and R_(III) is selected from the group consisting of:

[0064] (i) a 4 to 8 membered substituted, or unsubstituted heterocyclicring containing from 1 to 3 hetero atoms; and

[0065] (ii) linear or branched, saturated or unsaturated, substituted orunsubstituted, cyclic or acyclic, aliphatic or aromatic hydrocarbonradicals having from about 1 to about 30 carbon atoms;

[0066] (b) provided that when R² is (ii) then either: (A) at least oneof R¹ is other than C₂ to C₃ alkylene; or (B) R² has from 6 to 30 carbonatoms, and with the further proviso that when R² has from 8 to 18 carbonatoms, R is other than C₁ to C₅ alkyl.

[0067] Other suitable components herein include organic polymers havingdispersant, anti-redeposition, soil release or other detergencyproperties invention in levels of from about 0.1% to about 30%,preferably from about 0.5% to about 15%, most preferably from about 1%to about 10% by weight of composition. Preferred anti-redepositionpolymers herein include acrylic acid containing polymers such as SokalanPA30, PA20, PA15, PA10 and Sokalan CP10 (BASF GmbH), Acusol 45N, 480N,460N (Rohm and Haas), acrylic acid/maleic acid copolymers such asSokalan CP5 and acrylic/methacrylic copolymers. Preferred soil releasepolymers herein include alkyl and hydroxyalkyl celluloses (U.S. Pat. No.4,000,093), polyoxyethylenes, polyoxypropylenes and copolymers thereof,and nonionic and anionic polymers based on terephthalate esters ofethylene glycol, propylene glycol and mixtures thereof.

[0068] Heavy metal sequestrants and crystal growth inhibitors aresuitable for use herein in levels generally from about 0.005% to about20%, preferably from about 0.1% to about 10%, more preferably from about0.25% to about 7.5% and most preferably from about 0.5% to about 5% byweight of composition, for example diethylenetriamine penta (methylenephosphonate), ethylenediamine tetra(methylene phosphonate)hexamethylenediamine tetra(methylene phosphonate), ethylenediphosphonate, hydroxy-ethylene-1,1-diphosphonate, nitrilotriacetate,ethylenediaminotetracetate, ethylenediamine-N,N′-disuccinate in theirsalt and free acid forms.

[0069] The compositions herein can contain a corrosion inhibitor such asorganic silver coating agents in levels of from about 0.05% to about10%, preferably from about 0.1% to about 5% by weight of composition(especially paraffins such as Winog 70 sold by Wintershall, Salzbergen,Germany), nitrogen-containing corrosion inhibitor compounds (for examplebenzotriazole and benzimadazole—see GB-A-1137741) and Mn(II) compounds,particularly Mn(II) salts of organic ligands in levels of from about0.005% to about 5%, preferably from about 0.01% to about 1%, morepreferably from about 0.02% to about 0.4% by weight of the composition.

[0070] Other suitable components herein include colorants, water-solublebismuth compounds such as bismuth acetate and bismuth citrate at levelsof from about 0.01% to about 5%, enzyme stabilizers such as calcium ion,boric acid, propylene glycol and chlorine bleach scavengers at levels offrom about 0.01% to about 6%, lime soap dispersants (see WO-A-93/08877),suds suppressors (see WO-93/08876 and EP-A-0705324), polymeric dyetransfer inhibiting agents, optical brighteners, perfumes, fillers andclay.

[0071] Liquid detergent compositions can contain low quantities of lowmolecular weight primary or secondary alcohols such as methanol,ethanol, propanol and isopropanol can be used in the liquid detergent ofthe present invention. Other suitable carrier solvents used in lowquantities includes glycerol, propylene glycol, ethylene glycol,1,2-propanediol, sorbitol and mixtures thereof.

EXAMPLES

[0072] Abbreviations used in Examples In the examples, the abbreviatedcomponent identifications have the following meanings: CarbonateAnhydrous sodium carbonate STPP Sodium tripolyphosphate anhydrous(anhydrous) STPP Sodium tripolyphosphate hydrated to approximately 8%(hydrated) Silicate Amorphous Sodium Silicate (SiO₂:Na₂O = from 2:1 to4:1) HEDP Ethane 1-hydroxy-1,1-diphosphonic acid Perborate Sodiumperborate monohydrate Percarbonate Sodium percarbonate of the nominalformula 2Na₂CO₃.3H₂O₂ Termamyl α-amylase available from Novo Nordisk A/SSavinase protease available from Novo Nordisk A/S FN3 protease availablefrom Genencor SLF18 low foaming surfactant available from OlinCorporation ACNI alkyl capped non-ionic surfactant of formula C_(9/11)H_(19/23) EO₈-cyclohexyl acetal C₁₄AO tetradecyl dimethyl amine oxideC₁₆AO hexadecyl dimethyl amine oxide Duramyl α-amylase available fromNovo Nordisk A/S DPG dipropylene glycol

[0073] In the following examples all levels are quoted as parts byweight.

Examples 1 to 4

[0074] The compositions of examples 1 to 4 are made in the form of a twocompartment PVA pouch. The dual compartment pouch is made from a MonosolM8630 film as supplied by Chris-Craft Industrial Products. The pouchesmade by presealing the liquid composition using the technique describedhereinabove. The particulate composition and the anhydrous compositionare placed in two different horizontal layered compartments, theanhydrous composition being placed above the particulate composition.The exemplified pouches show a good stability of the particulateautomatic dishwashing product. Example 1 2 3 4 Particulate compositionC₁₄AO 5.55 5.55 C₁₆AO 5.55 5.55 ACNI 5.55 5.55 SLF18 5.55 5.55 STPP(anhydrous) 21.0 21.0 21.0 21.0 STPP (hydrated) 31.5 31.5 31.5 31.5 HEDP1.0 1.0 1.0 1.0 Savinase 0.7 0.7 0.7 0.7 Termamyl 0.7 0.7 0.7 0.7Perborate 13.55 13.55 Percarbonate 13.55 13.55 Carbonate 15.0 10.0 15.015.0 Silicate 5.0 10.0 5.0 5.0 Perfume 0.5 0.5 0.5 0.5 Anhydrouscomposition DPG 99.5 95.0 95.0 99.5 FN3 Liquid 2.60 2.4 Duramyl Liquid2.0 2.4 Dye 0.5 0.4 0.2 0.5

Examples 5 to 8

[0075] The particulate compositions of examples 1 to 4 are formed intotablets. The tablets are prepared as follows. The detergent compositionis prepared by admixing the granular and liquid components and is thenpassed into the die of a conventional rotary press. The press includes apunch suitably shaped for forming a mould in the upper surface of thetablet. The cross-section of the die is approximately 30×38 mm. Thecomposition is then subjected to a compression force of 940 kg/cm², thepunch is elevated, and a tablet comprising the mould is ejected from thetablet press.

[0076] Separately, PVA pouches are formed and filled with the anhydrousauxiliary compositions of examples 1 to 4.

[0077] The multi-compartment pouches are made by placing PVA film into atray having a series of tablet-shaped depresions. The tray is filledwith tablets, the tablets being positioned into the tray such that thetablet moulds are facing upwards. A layer of pouches comprising theanhydrous composition is placed with the pouches over and adjacent themoulds of the tablets and is used to close, by solvent sealing, thelayer of open pouches comprising the tablets.

[0078] Monosol M8630 film as supplied by Chris-Craft Industrial Productswas used to make the pouches.

[0079] The exemplified pouches show a good stability of the particulateautomatic dishwashing product.

1. A method of washing dishware/tableware in an automatic dishwashingmachine, said method comprising the steps of contacting saiddishware/tableware and simultaneously or sequentially deliveringquantities of a particulate or densified particulate automaticdishwashing product and of an anhydrous liquid, gel or paste form of adishwashing detergent auxiliary contained in separate compartments of amulti-compartment pouch into the same or different cycles of thedishwashing machine.
 2. A method according to claim 1 wherein saidparticulate dishwashing product is densified by a method selected fromthe group consisting of tamping, compression, the application ofinertial force, compaction, and combinations thereof
 3. A methodaccording to claim 1 wherein said particulate dishwashing product is inthe form of a tablet.
 4. A method according to claim 1 wherein saidparticulate dishwashing product comprises one or more moisture-sensitivedetergent actives and wherein said detergent auxiliary comprises ahumectant in levels sufficient to act as a moisture sink for stabilizingthe moisture-sensitive detergent active.
 5. A method according to claim4 wherein said humectant is a non-aqueous hydrophilic organic solventselected from the group consisting of glycols, polyhydric alcohols, andmixtures thereof.
 6. A method according to claim 4 wherein saidmoisture-sensitive detergent active is a detergency bleach.
 7. A methodaccording to claim 1 wherein said anhydrous detergent auxiliarycomprises a detergency enzyme.
 8. A method according to claim 1 whereinsaid anhydrous detergent auxiliary comprises an organic solvent systemeffective in removing cooked-, baked- and burnt-on soils.
 9. A methodaccording to claim 8 wherein said organic solvent system is selectedfrom the group consisting of alcohols, amines, esters, glycol ethers,glycols, terpenes, and mixtures thereof.
 10. A method according to claim8 wherein said organic solvent system is selected from the groupconsisting of organoamine solvents, alcoholic solvents, glycols, glycolderivatives, and mixtures thereof; wherein said organoamine solvents areselected from the group consisting of alkanolamines, alkylamines,alkyleneamines, and mixtures thereof; wherein said alcoholic solventsare selected from the group consisting of aromatic alcohols, aliphaticalcohols, cycloaliphatic alcohols, and mixtures thereof; and whereinsaid glycols and glycol derivatives are selected from the groupconsisting of C₂-C₃ (poly)alkylene glycols, glycol ethers, glycolesters, and mixtures thereof.
 11. A method according to claim 8 whereinsaid organic solvent comprises organoamine solvent and glycol ethersolvent in a weight ratio of from about 3:1 to about 1:3.
 12. A methodaccording to claim 11 wherein said glycol ether solvent is selected fromthe group consisting of ethylene glycol monobutyl ether, diethyleneglycol monobutyl ether, ethylene glycol monomethyl ether, ethyleneglycol monoethyl ether, diethylene glycol monomethyl ether, diethyleneglycol monoethyl ether, propylene glycol monobutyl ether, dipropyleneglycol monobutyl ether, ethylene glycol phenyl ether, and mixturesthereof.
 13. A method according to claim 1 wherein the detergentauxiliary is in the form of a paste having a density greater than about1100 Kg/m³.
 14. A method according to claim 1 wherein the pouch is watersoluble.
 15. A method according to claim 1 wherein the compartments ofthe multi-compartment pouch have different rates of solubility in waterunder given temperature conditions.
 16. A method according to claim 1wherein the anhydrous detergent auxiliary composition comprises anon-ionic surfactant.